WO2011099583A1 - 立体選択的オレフィン重合用触媒及び立体選択的ポリオレフィンの製造方法 - Google Patents
立体選択的オレフィン重合用触媒及び立体選択的ポリオレフィンの製造方法 Download PDFInfo
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- WO2011099583A1 WO2011099583A1 PCT/JP2011/052937 JP2011052937W WO2011099583A1 WO 2011099583 A1 WO2011099583 A1 WO 2011099583A1 JP 2011052937 W JP2011052937 W JP 2011052937W WO 2011099583 A1 WO2011099583 A1 WO 2011099583A1
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- YKRCKUBKOIVILO-PHDIDXHHSA-N (1r,2r)-cyclohexane-1,2-dithiol Chemical compound S[C@@H]1CCCC[C@H]1S YKRCKUBKOIVILO-PHDIDXHHSA-N 0.000 description 1
- JWZGJDATMFMKIO-UHFFFAOYSA-N (2,3,4-trifluorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(F)C(F)=C1F JWZGJDATMFMKIO-UHFFFAOYSA-N 0.000 description 1
- OUHOZBRDLAZZLQ-UHFFFAOYSA-N (2,3,5,6-tetrafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=CC(F)=C1F OUHOZBRDLAZZLQ-UHFFFAOYSA-N 0.000 description 1
- FWUHUNUOUDQTFG-UHFFFAOYSA-N (3,4,5-trifluorophenoxy)boronic acid Chemical compound OB(O)OC1=CC(F)=C(F)C(F)=C1 FWUHUNUOUDQTFG-UHFFFAOYSA-N 0.000 description 1
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- JBVMSEMQJGGOFR-FNORWQNLSA-N (4e)-4-methylhexa-1,4-diene Chemical compound C\C=C(/C)CC=C JBVMSEMQJGGOFR-FNORWQNLSA-N 0.000 description 1
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- QVLAWKAXOMEXPM-DICFDUPASA-N 1,1,1,2-tetrachloro-2,2-dideuterioethane Chemical compound [2H]C([2H])(Cl)C(Cl)(Cl)Cl QVLAWKAXOMEXPM-DICFDUPASA-N 0.000 description 1
- FMZITCJWMYHQFG-UHFFFAOYSA-N 1,2,3,4,4a,5,8,8a-octahydro-2-methyl-1,4:5,8-dimethanonaphthalene Chemical compound C1C(C23)C=CC1C3C1CC2CC1C FMZITCJWMYHQFG-UHFFFAOYSA-N 0.000 description 1
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- NIMLCWCLVJRPFY-UHFFFAOYSA-N 1-(5-bicyclo[2.2.1]hept-2-enyl)ethanone Chemical compound C1C2C(C(=O)C)CC1C=C2 NIMLCWCLVJRPFY-UHFFFAOYSA-N 0.000 description 1
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- DRWRVXAXXGJZIO-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enyl acetate Chemical compound C1C2C(OC(=O)C)CC1C=C2 DRWRVXAXXGJZIO-UHFFFAOYSA-N 0.000 description 1
- YSWATWCBYRBYBO-UHFFFAOYSA-N 5-butylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCC)CC1C=C2 YSWATWCBYRBYBO-UHFFFAOYSA-N 0.000 description 1
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 description 1
- VSQLAQKFRFTMNS-UHFFFAOYSA-N 5-methylhexa-1,4-diene Chemical compound CC(C)=CCC=C VSQLAQKFRFTMNS-UHFFFAOYSA-N 0.000 description 1
- PGNNHYNYFLXKDZ-UHFFFAOYSA-N 5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CC=CC=C1 PGNNHYNYFLXKDZ-UHFFFAOYSA-N 0.000 description 1
- UCKITPBQPGXDHV-UHFFFAOYSA-N 7-methylocta-1,6-diene Chemical compound CC(C)=CCCCC=C UCKITPBQPGXDHV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OXPBJFKLXDYFAU-UHFFFAOYSA-N CC1C=CC=C1.[C-]1(C=CC=C1)C.[Fe+2] Chemical compound CC1C=CC=C1.[C-]1(C=CC=C1)C.[Fe+2] OXPBJFKLXDYFAU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- BMAXQTDMWYDIJX-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbonitrile Chemical group C1C2C(C#N)CC1C=C2 BMAXQTDMWYDIJX-UHFFFAOYSA-N 0.000 description 1
- PCGYNXNSBCFBSU-UHFFFAOYSA-N bis(2,3,4,5,6-pentafluorophenyl)-phenylborane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=CC=CC=C1 PCGYNXNSBCFBSU-UHFFFAOYSA-N 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical compound [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical compound [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 description 1
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- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 1
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- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
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- CPDVHGLWIFENDJ-UHFFFAOYSA-N dihexylalumane Chemical compound C(CCCCC)[AlH]CCCCCC CPDVHGLWIFENDJ-UHFFFAOYSA-N 0.000 description 1
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- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- ORVACBDINATSAR-UHFFFAOYSA-N dimethylaluminum Chemical compound C[Al]C ORVACBDINATSAR-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- KNLGRGALOHHVOL-UHFFFAOYSA-N hafnium(4+);methanidylbenzene Chemical compound [Hf+4].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 KNLGRGALOHHVOL-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
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- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
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- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 239000012968 metallocene catalyst Substances 0.000 description 1
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- NOUWNNABOUGTDQ-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2+] NOUWNNABOUGTDQ-UHFFFAOYSA-N 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 239000012005 post-metallocene catalyst Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940054334 silver cation Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- BMKAZNZYKFHZCV-UHFFFAOYSA-N tris(2,3,4-trifluorophenyl)borane Chemical compound FC1=C(F)C(F)=CC=C1B(C=1C(=C(F)C(F)=CC=1)F)C1=CC=C(F)C(F)=C1F BMKAZNZYKFHZCV-UHFFFAOYSA-N 0.000 description 1
- GZQXROYFQLBBPK-UHFFFAOYSA-N tris(2,3,5,6-tetrafluorophenyl)borane Chemical compound FC1=CC(F)=C(F)C(B(C=2C(=C(F)C=C(F)C=2F)F)C=2C(=C(F)C=C(F)C=2F)F)=C1F GZQXROYFQLBBPK-UHFFFAOYSA-N 0.000 description 1
- GIIXTFIYICRGMZ-UHFFFAOYSA-N tris(2,3-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C(=C(C)C=CC=2)C)C=2C(=C(C)C=CC=2)C)=C1C GIIXTFIYICRGMZ-UHFFFAOYSA-N 0.000 description 1
- LKNHGIFPRLUGEG-UHFFFAOYSA-N tris(3,4,5-trifluorophenyl)borane Chemical compound FC1=C(F)C(F)=CC(B(C=2C=C(F)C(F)=C(F)C=2)C=2C=C(F)C(F)=C(F)C=2)=C1 LKNHGIFPRLUGEG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/16—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Definitions
- the present invention relates to a stereoselective olefin polymerization catalyst using a hafnium complex and a method for producing a stereoselective polyolefin using the catalyst.
- metallocene catalysts has been one of the topics in the chemistry of olefin polymerization that has been greatly developed by Ziegler-Natta type magnesium-supported highly active titanium catalysts. Further, recently, development of so-called post metallocene catalysts has attracted attention as a catalyst for constructing a more precise polymerization process.
- Non-Patent Documents 5 and 6 in Germany synthesized a Group 4 metal complex using a ligand in which the nitrogen atom of the tetradentate ligand was replaced with a sulfur atom.
- it is expanding to stereoselective polymerization of ⁇ -olefins.
- stereoselective polymerization reaction of ⁇ -olefin was not achieved.
- C 2 symmetry of the active centers in the reactions for structural flexibility of cationic species are prepared using a co-catalyst from the complexes (the catalytically active species in the polymerization of ⁇ - olefins) was thought to be lost. Therefore, development of new ligands and catalysts having high activity while maintaining C 2 symmetry is required.
- Patent Document 1 reports a method of polymerizing propylene using diphenoxy titanium, zirconium or hafnium complex derived from ethane-1,2-dithiol.
- the present inventor has reported diphenoxy titanium, zirconium and hafnium complexes derived from trans-cyclooctane-1,2-dithiol (Non-patent Document 7), and among these complexes, a zirconium complex was used as a catalyst.
- Reported a method for polymerizing 1-hexene (Non-patent Document 8).
- Patent Document 1 The entire description of Patent Document 1 and Non-Patent Document 1-8 is specifically incorporated herein by reference.
- Non-Patent Document 8 the diphenoxyzirconium complex derived from trans-cyclooctane-1,2-dithiol described in Non-Patent Document 8 enables polymerization with high activity and high isoselectivity. It has been desired to provide a catalyst that produces a high molecular weight polymer and enables isoselective polymerization, and a method for producing a stereoselective polyolefin using the catalyst.
- an object of the present invention is to produce a polymer having a much higher molecular weight than that of a diphenoxyzirconium complex derived from trans-cyclooctane-1,2-dithiol described in Non-Patent Document 8, and has a high isoselectivity.
- a catalyst capable of producing a stereoselective polyolefin having a low dispersion (Mw / Mn) and a sharp molecular weight distribution, and a method for producing a stereoselective polyolefin using this catalyst. is there.
- the present inventor has found that the above-described problems can be solved by the present invention through intensive studies.
- a highly isoselective polymerization that produces a polymer having a significantly higher molecular weight.
- a catalyst capable of producing a stereoselective polyolefin having a small dispersion (Mw / Mn) and a sharp molecular weight distribution compared to the diphenoxyzirconium complex derived from trans-cyclooctane-1,2-dithiol described in Non-Patent Document 8, a highly isoselective polymerization that produces a polymer having a significantly higher molecular weight.
- a catalyst capable of producing a stereoselective polyolefin having a small dispersion (Mw / Mn) and a sharp molecular weight distribution Mw / Mn
- this catalyst by using this catalyst, it is possible to produce a polyolefin having a high molecular weight, a low dispersion (Mw / Mn), and a sharp molecular weight distribution by performing polymerization with high isoselectivity. .
- Example 6 The chromatogram of GPC of the poly (1-hexene) obtained in Example 6 is shown.
- the GPC chromatogram of the poly (1-hexene) obtained in Example 8 is shown.
- the 13 C-NMR spectrum which investigated the stereoselectivity of the poly (1-hexene) obtained in Example 6 is shown.
- the 13 C-NMR spectrum which investigated the stereoselectivity of the poly (1-hexene) obtained in Example 8 is shown.
- 2 shows a GPC chromatogram of poly (4-methyl-1-pentene) obtained in Example 11.
- FIG. 2 shows a GPC chromatogram of poly (4-methyl-1-pentene) obtained in Example 12.
- the 13 C-NMR spectrum which investigated the stereoselectivity of the poly (4-methyl-1- pentene) obtained in Example 11 is shown.
- the 13 C-NMR spectrum which investigated the stereoselectivity of the poly (4-methyl-1- pentene) obtained in Example 12 is shown.
- the present invention relates to a stereoselective olefin polymerization catalyst containing a complex represented by the following formula (1).
- R 1 and R 2 are each independently an optionally substituted alkyl group or a halogen atom
- L is a ligand represented by CH 2 R 3 , a halogen atom, OR 4 , or NR 5 R 6.
- R 3 is a hydrogen atom, an aromatic group, or a trialkylsilyl group
- R 4 is a lower alkyl group having 1 to 6 carbon atoms
- R 5 and R 6 are each independently a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms.
- n 2 or 3, but preferably 3.
- R 1 and R 2 are independently an alkyl group which may have a substituent or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), and the alkyl group preferably has 1 to 30 carbon atoms
- An alkyl group more preferably an alkyl group having 1 to 12 carbon atoms.
- Specific examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, and an adamantyl group. .
- Examples of the substituent that the alkyl group has include a lower alkyl group having 1 to 6 carbon atoms, a phenyl group that may have a substituent, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).
- Examples of the substituent that the phenyl group may have include a lower alkyl group having 1 to 6 carbon atoms or a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom).
- Two R 1 s may be the same or different, and two R 2 may be the same or different.
- R 1 and R 2 are preferably an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, still more preferably an alkyl group having 1 to 12 carbon atoms, most preferably a t-butyl group, A cyclohexyl group and a 1-adamantyl group.
- L is CH 2 R 3 (methyl group optionally having substituent R 3 ), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), OR 4 (alkoxy group), or NR 5 R 6 ( An amino group optionally having substituents R 5 and R 6 .
- R 3 is a hydrogen atom, an aromatic group, or a trialkylsilyl group. Examples of the aromatic group for R 3 include a phenyl group, a 4-methoxyphenyl group, a 4-fluorophenyl group, a 4-chlorophenyl group, and a 4-bromophenyl group.
- the alkyl of the trialkylsilyl group can be a lower alkyl group having 1 to 6 carbon atoms, and examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a triisopropylsilyl group.
- R 4 is a lower alkyl group having 1 to 6 carbon atoms.
- the lower alkyl group include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, and a cyclohexyl group.
- R 5 and R 6 are each independently a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms.
- the lower alkyl group include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, and a cyclohexyl group.
- L is preferably CH 2 R 3 , a halogen atom or OR 4 , more preferably CH 2 R 3 or a halogen atom, still more preferably a methyl group, benzyl group, trimethylsilylmethyl group, chlorine atom, bromine An atom, most preferably a methyl group, a benzyl group, or a chlorine atom.
- the benzyl group directly bonded to the hafnium atom of these compounds was changed to a fluorine atom, chlorine atom, bromine atom, iodine atom, dimethylamino group, diethylamino group, methoxy group, ethoxy group, t-butoxy group, etc.
- the compound include compounds in which the 8-membered ring portion is changed to a 7-membered ring.
- the complex represented by the general formula (1) can be produced by the following steps using the compounds represented by the general formulas (2) and (3) as starting materials.
- Step 1 The tetradentate ligand represented by the compound (4) can be synthesized by the methods described in Non-Patent Documents 7 and 8, for example.
- N, R 1 and R 2 in the compounds (3) and (4) are the same as those in the general formula (1).
- trans-cycloheptane-1,2-dithiol or trans-cyclooctane-1,2-dithiol corresponding to compound (2) for example, 2.0 to 4.0 equivalents, preferably 2.0 to 2.5
- 3,5-disubstituted-2-hydroxybenzyl bromide corresponding to an equivalent amount of compound (3) the corresponding compound represented by formula (4) can be synthesized.
- Examples of 3,5-disubstituted-2-hydroxybenzyl bromide include the following. These compounds are known compounds.
- This reaction can be performed under air, helium, argon or nitrogen stream.
- it is under a helium, argon or nitrogen stream, more preferably under a nitrogen or argon stream.
- the temperature at which the compound represented by formula (2) and the compound represented by formula (3) are reacted is, for example, in the temperature range of ⁇ 100 ° C. to 100 ° C., preferably in the temperature range of ⁇ 80 ° C. to 80 ° C. is there. However, it is not intended to be limited to this range.
- the time for reacting the compound represented by the formula (2) and the compound represented by the formula (3) is, for example, 1 minute to 24 hours, preferably 5 minutes to 20 hours, more preferably 30 minutes to 18 hours. It is. However, it is not intended to be limited to this range.
- L in the compound (5) is CH 2 R 3 (methyl group optionally having substituent R 3 ), halogen atom (chlorine atom, bromine atom, iodine atom), OR 4 (alkoxy group) as described above. Group), NR 5 R 6 (amino group optionally having substituents R 5 and R 6 ).
- HFL 4 for example, Hf (CH 2 Ph) 4 , Hf (CH 2 SiMe 3) 4, HfF 4, HfCl 4, HfBr 4, HfI 4, Hf (OMe) 4, Hf (OEt) 4, Hf (Oi -Pr) 4 , Hf (On-Bu) 4 , Hf (Oi-Bu) 4 , Hf (Ot-Bu) 4 , Hf (NMe 2 ) 4 , Hf (NEt 2 ) 4 and the like.
- this reaction is preferably carried out in a helium, argon or nitrogen stream, more preferably in a nitrogen or argon stream.
- the temperature at which the compound represented by the formula (4) and the compound represented by the formula (5) are reacted is, for example, a temperature range of ⁇ 100 ° C. to 100 ° C., preferably ⁇ 80 ° C. to There is a temperature range of 50 ° C. However, it is not intended to be limited to this range.
- the time for reacting the compound represented by the formula (5) with the base is, for example, 1 minute to 24 hours, preferably 5 minutes to 12 hours, more preferably 30 minutes to 3 hours. . However, it is not intended to be limited to this range.
- the compound represented by the formula (5) is HfF 4, HfCl 4, HfBr 4, HFI 4
- a base for example an organolithium reagent, Grignard reagents, metal hydride such as, Specifically, n-butyllithium, sec-butyllithium, t-butyllithium, lithium hydride, sodium hydride, potassium hydride, etc. are reacted to obtain a reaction product, and the reaction product contains HfF 4 , HfCl It is possible to synthesize by adding any of 4 , HfBr 4 , and HfI 4 .
- the temperature at which the compound represented by the formula (4) is reacted with the base and the compound represented by the formula (5) is, for example, in the temperature range of ⁇ 100 ° C. to 150 ° C. Yes, preferably in the temperature range of ⁇ 80 ° C. to 50 ° C. However, it is not intended to be limited to this range.
- the time for reacting the compound represented by the formula (4) with the base and the compound represented by the formula (5) is, for example, 1 minute to 24 hours, preferably The time is 5 minutes to 12 hours, more preferably 30 minutes to 3 hours. However, it is not intended to be limited to this range.
- the complex represented by the general formula (1) obtained above is reacted with an organolithium reagent or Grignard reagent to synthesize a complex in which L of the complex represented by the general formula (1) is CH 2 R 3. You can also.
- the solvent used in this reaction is not particularly limited as long as it is a solvent generally used in similar reactions, and examples thereof include a hydrocarbon solvent or an ether solvent, preferably toluene, benzene, o-xylene, m-xylene, p-xylene, hexane, pentane, heptane, cyclohexane, diethyl ether or tetrahydrofuran, more preferably diethyl ether, toluene, tetrahydrofuran, hexane, pentane, heptane or cyclohexane.
- a hydrocarbon solvent or an ether solvent preferably toluene, benzene, o-xylene, m-xylene, p-xylene, hexane, pentane, heptane, cyclohexane, diethyl ether or tetrahydrofuran, more preferably
- the complex represented by the general formula (1) of the present invention described above is used as a polymerization catalyst component in the production of a polymer by homopolymerization of a polymerizable monomer or copolymerization of two or more polymerizable monomers. used. Preferably, it is homopolymerization.
- a polymerization catalyst obtained by bringing the complex represented by the general formula (1) of the present invention and the promoter component (A) into contact with each other is used.
- the promoter component is not particularly limited as long as it activates the complex represented by the general formula (1) of the present invention and enables polymerization.
- (A-1) Organoaluminum compound (A-2) It may contain at least one compound selected from the group consisting of boron compounds.
- (A-1)) As the compound (A-1) used in the present invention, a known organoaluminum compound can be used.
- (A-1-1) an organoaluminum compound represented by the general formula E 1 a AlY 1 3-a , (A-1-2) a general formula ⁇ —Al (E 2 ) —O— ⁇ b
- Y 1 represents a hydrogen atom or a halogen atom, and all Y 1 may be the same or different, a is an integer of 0 ⁇ a ⁇ 3, b is an integer of 2 or more, and c is 1 or more. Any one of them, or a mixture of 2 to 3 thereof.
- organoaluminum compound (A-1-1) represented by the general formula E 1 a AlY 1 3-a include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum and the like.
- Dialkylaluminum chlorides such as alkylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride, etc.
- Alkyl aluminum dichloride dimethylaluminum Arm hydride, diethylaluminum hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride.
- dialkyl aluminum hydride such as dihexyl aluminum hydride.
- Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are more preferable.
- E 2 and E 3 in the linear aluminoxane (A-1-3) having the structure represented by 2 are methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group. And alkyl groups such as isobutyl group, n-pentyl group and neopentyl group.
- b is an integer of 2 or more
- c is an integer of 1 or more.
- E 2 and E 3 are a methyl group and an isobutyl group, b is 2 to 40, and c is 1 to 40.
- aluminoxane can be made by various methods. There is no restriction
- an aluminoxane is prepared by bringing a solution obtained by dissolving a trialkylaluminum (for example, trimethylaluminum) in an appropriate organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.) into contact with water.
- a trialkylaluminum for example, trimethylaluminum
- an appropriate organic solvent benzene, toluene, aliphatic hydrocarbon, etc.
- the method of making aluminoxane by making trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.
- (A-1-2) the general formula ⁇ -Al (E 2 ) -O— ⁇ b obtained by the above method and a cyclic aluminoxane having a structure represented by the formula (A-1-3)
- the linear aluminoxane having a structure represented by E 3 ⁇ —Al (E 3 ) —O— ⁇ c AlE 3 2 may be used after distilling off the volatile components if necessary. Further, the compound obtained by distilling off the volatile components and drying may be washed with an appropriate organic solvent (benzene, toluene, aliphatic hydrocarbon, etc.) and dried again.
- the compound (A-2) includes (A-2-1) a boron compound represented by the general formula BR 11 R 12 R 13 , (A-2-2) a general formula W + (BR 11 R 12 using either the boron compound represented - R 13 R 14) - a boron compound represented by, (a-2-3) general formula (V-H) + (BR 11 R 12 R 13 R 14) .
- R 11 to R 13 are halogen atoms, 1 to 20 Hydrocarbyl group containing 1 to 20 carbon atoms, halogenated hydrocarbyl group containing 1 to 20 carbon atoms, substituted silyl group containing 1 to 20 carbon atoms, alkoxy group containing 1 to 20 carbon atoms Or a disubstituted amino group containing 2 to 20 carbon atoms, which may be the same or different.
- Preferred R 11 to R 13 are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.
- (A-2-1) include triphenylborane, tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5). -Tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, etc. Triphenylborane and tris (pentafluorophenyl) borane are preferable.
- W + is an inorganic or organic cation
- B is a trivalent valence state. It is a boron atom
- R 11 to R 14 are the same as R 11 to R 13 in the above (A-2-1). That is, R 11 to R 14 include a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, a halogenated hydrocarbyl group containing 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
- a substituted silyl group, an alkoxy group containing 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms which may be the same or different.
- Preferred R 11 to R 14 are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.
- Examples of the inorganic cation W + include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation.
- Examples of the organic cation W + include a triphenylcarbenium cation. (BR 11 R 12 R 13 R 14 ) — includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro).
- Phenyl) borate tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis [3,5-bis (Trifluoromethyl) phenyl] borate and the like.
- Specific examples of the compound represented by the general formula W + (BR 11 R 12 R 13 R 14 ) — include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluoro). Phenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis [3,5-bis (trifluoromethyl) phenyl] borate, etc. Is most preferably triphenylcarbenium tetrakis (pentafluorophenyl) borate.
- R 11 to R 14 are the same as R 11 to R 13 in (A-2-3) above. That is, R 11 to R 14 include a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, a halogenated hydrocarbyl group containing 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
- a substituted silyl group, an alkoxy group containing 1 to 20 carbon atoms or a disubstituted amino group containing 2 to 20 carbon atoms which may be the same or different.
- Preferred R 11 to R 14 are a halogen atom, a hydrocarbyl group containing 1 to 20 carbon atoms, and a halogenated hydrocarbyl group containing 1 to 20 carbon atoms.
- Examples of (VH) + that is a Bronsted acid include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like (BR 11 R 12 R 13 R 14 ) ⁇ Is the same as described above.
- the contact of the complex represented by (1), the cocatalyst component As long as the catalyst is brought into contact and a catalyst is formed, any means may be used.
- the complex represented by (1) and the cocatalyst component can be separately supplied to the polymerization tank and brought into contact with each other in the polymerization tank.
- the co-catalyst component may be used in combination of a plurality of types, but some of them may be mixed and used in advance, or separately supplied to the polymerization tank and used. Good.
- the amount of each component used is usually such that the molar ratio of (A-1) to the complex represented by the general formula (1) is 0.01 to 10,000, preferably 1 to 5,000, represented by the general formula (1). It is desirable to use each component so that the molar ratio of (A-2) to the complex is 0.01 to 100, preferably 1.0 to 50.
- the concentration when each component is supplied in a solution state or suspended or slurried in a solvent is determined depending on the performance of the apparatus for supplying each component to the polymerization reactor, etc.
- the complex represented by the general formula (1) is usually 0.0001 to 10000 mmol / L, more preferably 0.001 to 1000 mmol / L, still more preferably, 0.01 to 100 mmol / L
- (A-1) is usually 0.01 to 10000 mmol / L, more preferably 0.05 to 5000 mmol / L, and still more preferably 0.1 to 0.1 mmol, in terms of Al atom.
- (A-2) is usually 0.001 to 500 mmol / L, more preferably 0.01 to 250 mmol / L, and still more preferably 0.05 to 100 mmol / L. Hope to use each component Arbitrariness.
- the olefin polymerization catalyst is an olefin polymerization catalyst obtained by contacting the complex represented by the general formula (1) with the above (A-1) and / or (A-2).
- (A-1) includes the above cyclic aluminoxane (A-1). -2) and / or linear aluminoxane (A-1-3) are preferred.
- Other preferred embodiments of the olefin polymerization catalyst include a complex represented by the general formula (1) and an olefin polymerization catalyst obtained by contacting (A-1) and (A-2).
- (A-1) is easy to use, and (A-2) is preferably (A-2-1) or (A-2-2).
- the method for producing a stereoselective polyolefin of the present invention is a method comprising polymerizing an olefin in the presence of the catalyst of the present invention.
- the olefin to polymerize may be single or plural, single is more preferable. If a single olefin is polymerized, a homopolymer is obtained, and if a plurality of olefins are polymerized, a copolymer is obtained.
- the olefin compound used for the polymerization is not particularly limited, but is preferably an olefin that exhibits desired physical properties by stereoselective polymerization.
- the olefin can be, for example, a monoolefin or a diolefin, with a monoolefin being preferred.
- monoolefins include 1-alkenes such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene ( It may be branched) And cyclopentene, cyclohexene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, Pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyl
- Ruken for example, 1,5-hexadiene, 1,4-hexadiene, 1,6-heptadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4- Hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, Norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1, 3-cyclohexadiene, butadiene,
- the monoolefin is preferably propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, more preferably propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, more preferably propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl -1-pentene.
- diolefin Preferably as diolefin, 1,5-hexadiene, 1,6-heptadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene, butadiene, more preferably 1,5-hexadiene, 1,6-heptadiene, 1,3-cyclohexadiene, butadiene.
- the polymerization method is not particularly limited.
- aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbons such as benzene and toluene, or halogenated hydrocarbons such as methylene dichloride.
- Solvent polymerization using carbon as a solvent, slurry polymerization, or the like is possible, and either continuous polymerization or batch polymerization is possible.
- the temperature and time of the polymerization reaction can be determined in consideration of the desired polymerization average molecular weight, the activity of the catalyst and the amount used.
- the polymerization temperature can usually be in the range of ⁇ 50 ° C.
- the polymerization time is appropriately determined depending on the kind of the target polymer and the reaction apparatus, but can usually be in the range of 1 minute to 20 hours, preferably in the range of 5 minutes to 18 hours. However, it is not intended to be limited to these ranges.
- a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.
- the concentration of each compound in the solvent is not particularly limited.
- the hafnium complex concentration in the solvent is, for example, in the range of 1 ⁇ 10 ⁇ 8 mmol / L to 10 mol / L
- the promoter concentration is, for example, in the range of 1 ⁇ 10 ⁇ 8 mmol / L to 10 mol / L. can do.
- the volume ratio of olefin: solvent can be in the range of 100: 0 to 1: 1000. However, these ranges are examples and are not intended to be limited to them. Even when no solvent is used, the concentration can be appropriately set with reference to the above range.
- the polymer obtained by polymerization can separate monomers when there is a solvent and unreacted monomers as follows.
- the monomer In the case of a viscous polymer, the monomer can be removed with a vacuum pump. However, this method cannot remove the catalyst.
- the monomer In the case of a solid polymer, the monomer can be removed by washing with methanol after the solvent is distilled off. With this method, the catalyst can be removed to some extent.
- Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) It measured on the following conditions by the gel permeation chromatography (GPC). A calibration curve was prepared using standard polystyrene. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
- the peak area of the peak was defined as the area of the signal in the range from the chemical shift of the valley with the adjacent peak on the high magnetic field side to the chemical shift of the valley with the adjacent peak on the low magnetic field side.
- ⁇ Calculation method 2, poly (4-methyl-1-pentene)> The peak area of a peak having a peak top in the vicinity of 45.61 to 45.66 ppm was determined.
- the peak area of the peak was defined as the area of the signal in the range from the chemical shift of the valley with the adjacent peak on the high magnetic field side to the chemical shift of the valley with the adjacent peak on the low magnetic field side.
- the formed precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure.
- Ether and saturated aqueous ammonium chloride solution were added to the resulting residue, and the ether layer was washed with water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure.
- the obtained residue was purified by silica gel column chromatography (developing solvent hexane-dichloromethane 1: 1) to obtain 6.74 g (yield 89%) of the title compound as colorless crystals.
- Table 1 summarizes the experimental conditions and the results of molecular weight measurement of the synthesized poly (1-hexene). The following experiment was performed in a glove box in an argon atmosphere, the molecular weight was determined by ⁇ Molecular Weight Measurement Condition 1>, and the regularity was determined by ⁇ Regularity Measurement Condition 1> and ⁇ Calculation Method 1>.
- Example 1 In a 50 mL Schlenk tube, 19.4 mg (0.020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium was added to 1 mL of benzene and hexane. dissolved in 5 mL, this solution tris 25 ° C. (pentafluorophenyl) borane [B (C 6 F 5) 3] 10.2mg of (0.020 mmol) was added and stirred for another 5 minutes.
- Example 2 In a 50 mL Schlenk tube, 19.4 mg (0.020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium was added to 1 mL of benzene and hexane. dissolved in 5 mL, this solution tris 25 ° C. (pentafluorophenyl) borane [B (C 6 F 5) 3] 10.2mg of (0.020 mmol) was added and stirred for another 5 minutes.
- Example 4 In a 50 mL Schlenk tube, dissolve 19.4 mg (0.020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium in 1 mL of benzene. To this solution, 10.2 mg (0.020 mmol) of tris (pentafluorophenyl) borane [B (C 6 F 5 ) 3 ] was added at 25 ° C., and the mixture was further stirred for 5 minutes.
- Example 5 In a 50 mL Schlenk tube, dissolve 19.4 mg (0.020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium in 1 mL of benzene. To this solution, 10.2 mg (0.020 mmol) of tris (pentafluorophenyl) borane [B (C 6 F 5 ) 3 ] was added at 25 ° C., and the mixture was further stirred for 5 minutes.
- Example 6 In a 50 mL Schlenk tube, dissolve 19.4 mg (0.020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium in 1 mL of benzene. To this solution, 10.2 mg (0.020 mmol) of tris (pentafluorophenyl) borane [B (C 6 F 5 ) 3 ] was added at 25 ° C., and the mixture was further stirred for 5 minutes.
- Example 7 In a 50 mL Schlenk tube, dissolve 19.4 mg (0.020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium in 5 mL of toluene. To this solution, 18.4 mg (0.020 mmol) of triphenylcarbenium tetrakis (pentafluorophenyl) borate [Ph 3 CB (C 6 F 5 ) 4 ] was added at 0 ° C., and the mixture was further stirred for 5 minutes.
- Example 8 In a 50 mL Schlenk tube, dissolve 19.4 mg (0.020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium in 5 mL of toluene. To this solution, 18.4 mg (0.020 mmol) of triphenylcarbenium tetrakis (pentafluorophenyl) borate [Ph 3 CB (C 6 F 5 ) 4 ] was added at 0 ° C., and the mixture was further stirred for 5 minutes.
- Table 2 summarizes the experimental conditions and the results of molecular weight measurement of the synthesized poly (4-methyl-1-pentene). The following experiment was performed in a glove box in an argon atmosphere, the molecular weight was determined by ⁇ Molecular Weight Measurement Condition 2>, and the regularity was determined by ⁇ Regularity Measurement Condition 2> and ⁇ Calculation Method 2>.
- Example 9 In a 50 mL Schlenk tube, 19.4 mg (0.020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium was added to 1 mL of benzene and hexane. dissolved in 5 mL, this solution tris 25 ° C. (pentafluorophenyl) borane [B (C 6 F 5) 3] 10.2mg of (0.020 mmol) was added and stirred for another 5 minutes.
- Example 11 In a 50 mL Schlenk tube, dissolve 19.4 mg (0.020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium in 5 mL of toluene. To this solution, triphenylcarbenium tetrakis (pentafluorophenyl) borate [Ph 3 CB (C 6 F 5 ) 4 ] was added at 25 ° C., and the mixture was further stirred for 5 minutes.
- Example 12 Dissolve 19.4 mg (0.020 mmol) of [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium in 5 mL of dichloromethane in a 50 mL Schlenk tube.
- triphenylcarbenium tetrakis (pentafluorophenyl) borate [Ph 3 CB (C 6 F 5 ) 4 ] was added at 25 ° C., and the mixture was further stirred for 10 minutes.
- Isotactic pentad fraction [mmmm]
- the isotactic pentad fraction is defined as A.I. Zambelli et al., “Macromolecules”, Vol. 6, 925 (1973), that is, isotactic linkage with pentad units in a crystalline polypropylene molecular chain measured using 13 C-NMR, in other words, 5 propylene monomer units. This is the fraction of propylene monomer units at the center of the chain that are continuously meso-bonded.
- a sample was prepared by uniformly dissolving about 200 mg of polymer in 3 mL of orthodichlorobenzene in a 10 mm ⁇ test tube, and the sample was measured by 13 C-NMR spectrum.
- Reference Example 8 (Preparation method of d-MMAO-3A) The same procedure as in Reference Example 7 was carried out except that the PMAO-S toluene solution (aluminum content 6.1 wt%) manufactured by Tosoh Finechem was changed to the MMAO-3A toluene solution (aluminum content 7.0 wt%) manufactured by Tosoh Finechem. .
- Reference Example 9 Method for preparing d-MMAO-4. The same procedure as in Reference Example 7 was carried out except that the PMAO-S toluene solution (aluminum content 6.1 wt%) manufactured by Tosoh Finechem was changed to the MMAO-4 toluene solution (aluminum content 7.4 wt%) manufactured by Tosoh Finechem. .
- Example 13 An autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 40 mL of toluene as a solvent and 80 g of propylene as a monomer were charged, and the temperature of the reactor was lowered to 0 ° C. After cooling, 118 mg of d-MAO was added, followed by [cyclooctanediyl-trans-1,2-bis (2-oxoyl-3,5-di-tert-butylbenzylsulfanyl)] dibenzylhafnium (1 ⁇ mol / mL , Toluene solution) 1 mL (1.0 ⁇ mol) was added to initiate polymerization.
- Example 14 The same procedure as in Example 13 was performed except that the polymerization temperature was 14 ° C.
- Example 15 The same procedure as in Example 13 was performed except that the polymerization temperature was 40 ° C.
- Example 16 The same procedure as in Example 13 was performed except that the polymerization temperature was 70 ° C.
- Example 17 The same procedure as in Example 13 was performed, except that d-MAO was changed to d-MMAO-3A at a polymerization temperature of 40 ° C.
- Example 18 The same procedure as in Example 13 was performed, except that d-MAO was changed to d-MMAO-4 and the polymerization temperature was 40 ° C.
- Example 19 An autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 40 mL of toluene as a solvent and 80 g of propylene as a monomer were charged, and the temperature of the reactor was lowered to 0 ° C.
- Example 20 The autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 40 mL of toluene as a solvent and 80 g of propylene as a monomer were charged, and the temperature of the reactor was increased to 40 ° C.
- Example 21 The autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 40 mL of toluene as a solvent and 80 g of propylene as a monomer were charged, and the temperature of the reactor was increased to 40 ° C.
- Example 23 The autoclave with a stirrer having an internal volume of 400 mL was vacuum dried and replaced with argon, and then 40 mL of toluene as a solvent and 80 g of 1-butene as a monomer were charged, and the reactor was heated to 40 ° C.
- the present invention is useful in the field relating to the production of stereoselective polyolefins.
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Abstract
Description
本発明者は、trans-シクロオクタン-1,2-ジチオールから誘導されるジフェノキシチタン、ジルコニウム及びハフニウム錯体を報告し(非特許文献7)、さらにこれらの錯体の内、ジルコニウム錯体を触媒として用いて1-ヘキセンを重合する方法を報告した(非特許文献8)。
本発明によれば、非特許文献8に記載のtrans-シクロオクタン-1,2-ジチオールから誘導されるジフェノキシジルコニウム錯体に比べて、格段に高分子量のポリマーを生成する高いアイソ選択的な重合を可能にし、かつ分散(Mw/Mn)が小さく、分子量分布がシャープな立体選択的ポリオレフィンを生成させることができる触媒を提供することができる。さらに、本発明によれば、この触媒を用いることで、高アイソ選択的に重合を行って、高分子量でかつ分散(Mw/Mn)が小さく、分子量分布がシャープなポリオレフィンを製造することができる。
(式中、nは2または3であり、
R1及びR2は、独立に、置換基を有してもよいアルキル基またはハロゲン原子であり、LはCH2R3、ハロゲン原子、OR4、またはNR5R6で示される配位子であり、
R3は水素原子、芳香族基、またはトリアルキルシリル基であり、
R4は炭素数1~6の低級アルキル基であり、
R5及びR6は独立に水素原子または炭素数1~6の低級アルキル基である。)
2つのR1はそれぞれ同一でも異なってもよいし、2つのR2はそれぞれ同一でも異なってもよい。
R1及びR2として好ましくはアルキル基であり、より好ましくは炭素数1~30のアルキル基であり、さらに好ましくは炭素数1~12のアルキル基であり、最も好ましくは、t-ブチル基、シクロヘキシル基、1-アダマンチル基である。
Lとして好ましくは、CH2R3、ハロゲン原子、OR4であり、より好ましくは、CH2R3、ハロゲン原子であり、さらに好ましくは、メチル基、ベンジル基、トリメチルシリルメチル基、塩素原子、臭素原子であり、最も好ましくはメチル基、ベンジル基、塩素原子である。
化合物(4)で示される四座配位子は、例えば、非特許文献7及び8に記載の方法により合成することができる。化合物(3)および(4)中のn、R1及びR2は、一般式(1)と同様である。
化合物(5)中のLは、上記と同様に、CH2R3(置換基R3を有してもよいメチル基)、ハロゲン原子(塩素原子、臭素原子、ヨウ素原子)、OR4(アルコキシ基)、NR5R6(置換基R5、R6を有してもよいアミノ基)で示される配位子である。
重合用触媒としては、上記の本発明の一般式(1)で表される錯体および助触媒成分(A)を接触させて得られる重合用触媒が用いられる。かかる助触媒成分は、上記の本発明の一般式(1)で表される錯体を活性化させ、重合可能とするものであれば特に制限はないが、
(A-1)有機アルミニウム化合物
(A-2)ホウ素化合物
よりなる群から選ばれる少なくとも1種の化合物を含んでいてもよい。
本発明において用いる化合物(A-1)としては、公知の有機アルミニウム化合物が使用できる。好ましくは、(A-1-1)一般式 E1a AlY1 3-a で表される有機アルミニウム化合物、(A-1-2)一般式 {-Al(E2 )-O-}b で表される構造を有する環状のアルミノキサン、及び(A-1-3)一般式 E3 {-Al(E3)-O-}c AlE3 2 で表される構造を有する線状のアルミノキサン(但し、E1 、E2 、E3 は、炭素数1~8のハイドロカルビル基であり、全てのE1 、全てのE2 及び全てのE3は同じであっても異なっていても良い。Y1は水素原子又はハロゲン原子を表し、全てのY1は同じであっても異なっていても良い。aは0<a≦3の整数で、bは2以上の整数を、cは1以上の整数を表す。)のうちのいずれか、あるいはそれらの2~3種の混合物を例示することができる。
本発明において化合物(A-2)としては、(A-2-1)一般式BR11 R12 R13で表されるホウ素化合物、(A-2-2)一般式W+ (BR11 R12R13 R14 )- で表されるホウ素化合物、(A-2-3)一般式(V-H)+ (BR11 R12 R13 R14)-で表されるホウ素化合物のいずれかを用いる。
本発明の立体選択的ポリオレフィンの製造方法は、上記本発明の触媒の存在下にオレフィンを重合させることを含む方法である。重合するオレフィンは単独でも複数でもよいが、単独がより好ましい。単独のオレフィンを重合すれば、単独重合体が得られ、複数のオレフィンを重合すれば、共重合体が得られる。重合に用いられるオレフィン化合物は特に制限はないが、立体選択的に重合することで、所望の物性を示すオレフィンであることが好ましい。オレフィンは、例えば、モノオレフィンまたはジオレフィンであることができるが、モノオレフィンが好ましい。モノオレフィンの例としては、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-ノネン、1-デセン、4-メチル-1-ペンテンなどの1-アルケン(枝分かれしていても良い)
及び、シクロペンテン、シクロヘキセン、5-メチルノルボルネン、5-エチルノルボルネン、5-ブチルノルボルネン、5-フェニルノルボルネン、5-ベンジルノルボルネン、テトラシクロドデセン、トリシクロデセン、トリシクロウンデセン、ペンタシクロペンタデセン、ペンタシクロヘキサデセン、8-メチルテトラシクロドデセン、8-エチルテトラシクロドデセン、5-アセチルノルボルネン、5-アセチルオキシノルボルネン、5-メトキシカルボニルノルボルネン、5-エトキシカルボニルノルボルネン、5-メチル-5-メトキシカルボニルノルボルネン、5-シアノノルボルネン、8-メトキシカルボニルテトラシクロドデセン、8-メチル-8-テトラシクロドデセン、8-シアノテトラシクロドデセン等などの環状アルケン等を挙げることができる。ジオレフィンとしては、例えば、
1,5-ヘキサジエン、1,4-ヘキサジエン、1,6-ヘプタジエン、1,4-ペンタジエン、1,7-オクタジエン、1,8-ノナジエン、1,9-デカジエン、4-メチル-1,4-ヘキサジエン、5-メチル-1,4-ヘキサジエン、7-メチル-1,6-オクタジエン、5-エチリデン-2-ノルボルネン、ジシクロペンタジエン、5-ビニル-2-ノルボルネン、5-メチル-2-ノルボルネン、ノルボルナジエン、5-メチレン-2-ノルボルネン、1,5-シクロオクタジエン、5,8-エンドメチレンヘキサヒドロナフタレン、1,3-ヘキサジエン、1,3-オクタジエン、1,3-シクロオクタジエン、1,3-シクロヘキサジエン、ブタジエン、等を挙げることができる。モノオレフィンとして好ましくはプロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-ノネン、1-デセン、4-メチル-1-ペンテンであり、より好ましくはプロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、1-デセン、4-メチル-1-ペンテンであり、さらに好ましくはプロピレン、1-ブテン、1-ペンテン、1-ヘキセン、4-メチル-1-ペンテンである。
ジオレフィンとして好ましくは、
1,5-ヘキサジエン、1,6-ヘプタジエン、5-エチリデン-2-ノルボルネン、ジシクロペンタジエン、5-ビニル-2-ノルボルネン、5-メチル-2-ノルボルネン、ノルボルナジエン、5-メチレン-2-ノルボルネン、1,5-シクロオクタジエン、1,3-シクロオクタジエン、1,3-シクロヘキサジエン、ブタジエンであり、より好ましくは、
1,5-ヘキサジエン、1,6-ヘプタジエン、1,3-シクロヘキサジエン、ブタジエンである。
重合反応の温度および時間は、所望の重合平均分子量と触媒の活性度および使用量を考慮して決定することができる。重合温度は通常、-50℃~200℃の範囲を取り得るが、特に、-20℃~100℃の範囲が好ましく、重合圧力は通常、常圧~50MPaが好ましい。重合時間は、一般的に、目的とするポリマーの種類、反応装置により適宜決定されるが通常、1分間~20時間の範囲、好ましくは5分間~18時間の範囲を取ることができる。但し、これらの範囲に制限される意図ではない。また、本発明は共重合体の分子量を調節するために水素等の連鎖移動剤を添加することもできる。
ゲルパーミエーションクロマトグラフィー(GPC)により、下記の条件で測定した。また、検量線は標準ポリスチレンを用いて作成した。分子量分布は重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)で評価した。
<分子量測定条件1、ポリ(1-ヘキセン)>
装置 東ソーHLC-8220 GPC apparatus
カラム TSKgel SuperHZM-H (10)4.6*150 3本
測定温度 40℃
溶媒 テトラヒドロフラン
サンプル濃度 2mg/2mL
<分子量測定条件2、ポリ(4-メチル-1-ペンテン)>
装置 東ソーHLC-8121GPC/HT apparatus
カラム TSKgel GMHHR-H(20) HT 7.8*300 3本
測定温度 145℃
溶媒 1,2-ジクロロベンゼン
サンプル濃度 5mg/5mL
カーボン核磁気共鳴法によって、次の測定条件により、カーボン核磁気共鳴スペクトル(13C-NMR)を測定し、下記算出方法より求めた。
<規則性測定条件1、ポリ(1-ヘキセン)>
装置 :JEOL社製 ECS400
測定溶媒:クロロホルム-d1
測定温度:25℃
測定方法:プロトンデカップリング法
パルス幅:30度
パルス繰り返し時間:2秒
測定基準:重クロロホルム中の残留クロロホルム
窓関数 :負の指数関数
<規則性測定条件2、ポリ(4-メチル-1-ペンテン)>
装置 :JEOL社製 ECS400
測定溶媒:テトラクロロエタン-d2
測定温度:130℃
測定方法:プロトンデカップリング法
パルス幅:30度
パルス繰り返し時間:2秒
測定基準:重テトラクロロエタン中の残留テトラクロロエタン
窓関数 :負の指数関数
<算出方法1、ポリ(1-ヘキセン)>
34.60~34.65ppm付近にピークトップを有するピークのピーク面積を求めた。当該ピークのピーク面積は、高磁場側で隣接するピークとの谷のケミカルシフトから、低磁場側で隣接するピークとの谷のケミカルシフトまでの範囲でのシグナルの面積とした。
<算出方法2、ポリ(4-メチル-1-ペンテン)>
45.61~45.66ppm付近にピークトップを有するピークのピーク面積を求めた。当該ピークのピーク面積は、高磁場側で隣接するピークとの谷のケミカルシフトから、低磁場側で隣接するピークとの谷のケミカルシフトまでの範囲でのシグナルの面積とした。
trans-1,2-ビス(2-ヒドロキシ-3,5-ジ-tert-ブチルベンジルスルファニル)シクロオクタンの合成
アルゴン雰囲気下、trans-シクロオクタン-1,2-ジチオール2.18g(12.4mmol)と臭化3,5-ジ-t-ブチル-2-ヒドロキシベンジル7.52g(25.1mmol)をテトラヒドロフラン80mLに溶かし0℃に冷却した。そこに、トリエチルアミン3.5mL(24.9mmol)を加え、0℃で1時間、室温で終夜攪拌した。生成した沈殿物を濾過して除き、濾液を減圧下濃縮した。得られた残渣にエーテルと飽和塩化アンモニウム水溶液を加え、エーテル層を水洗、無水硫酸マグネシウムで乾燥後、減圧下溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー(展開溶媒 ヘキサン-ジクロロメタン 1:1)で精製し無色結晶として表題化合物6.74g(収率89%)を得た。
融点:122-123℃ (ヘキサンより再結晶)
1H-NMR (400 MHz,δ,ppm, CDCl3)
1.12-1.94 (m, 48 H), 2.63-2.65 (m, 2 H), 3.81 (d, J= 13 Hz, 2 H), 3.90 (d, J= 13 Hz, 2 H), 6.92 (d, J= 2 Hz, 2 H), 6.95 (s, 2 H), 7.26 (d, J = 2 Hz, 2 H).
13C-NMR (100.7 MHz,δ, CDCl3)
25.7, 25.8, 29.8, 31.2, 31.6, 34.2, 35.0, 35.4, 49.6, 121.6, 123.7, 125.4, 137.4, 142.0, 152.2.
元素分析:計算値(C38H60O2S2)C, 74.45%; H, 9.87%.
実測値: C, 74.39%; H, 10.09%.
文献:A. Ishii, A. Ono, N. Nakata, J. Sulf. Chem. 2009, 30, 236-244.
trans-1,2-ビス(2-ヒドロキシ-3,5-ジ-tert-ブチルベンジルスルファニル)シクロヘキサンの合成
アルゴン雰囲気下、trans-シクロヘキサン-1,2-ジチオール1.08g(7.3mmol)と臭化3,5-ジ-t-ブチル-2-ヒドロキシベンジル4.58g(15.3mmol)をテトラヒドロフラン90mLに溶かし0℃に冷却した。そこに、トリエチルアミン2.13mL(15.3mmol)を加え、0℃で15時間攪拌した。生成した沈殿物を濾過で除き、濾液を減圧下濃縮した。得られた残渣にエーテルと希塩酸を加え、エーテル層を水洗、無水硫酸マグネシウムで乾燥後、減圧下溶媒を留去した。得られた残渣をシリカゲルカラムクロマトグラフィー(展開溶媒 ヘキサン-ジクロロメタン 1:1)で精製し無色結晶として表題化合物3.86g(収率90%)を得た。
融点:104-106℃ 分解(エタノールより再結晶)
1H-NMR (400 MHz,δ,ppm, CDCl3)
1.19-1.43 (m, 44 H), 2.09-2.15 (m, 2 H), 2.58-2.61 (m, 2 H), 3.79 (s, 4 H), 6.75 (s, 2 H), 6.93 (d, J = 2 Hz, 2 H), 7.25 (d, J = 2 Hz, 2 H).
13C-NMR (100.7 MHz,δ, CDCl3)
24.7, 29.7, 31.6, 32.6, 33.9, 34.2, 35.0, 48.1, 121.6, 123.7, 125.2, 137.3, 142.2, 152.0.
元素分析:計算値(C36H56O2S2)C, 73.92%; H, 9.34%.
実測値: C, 74.17%; H, 9.31%.
[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルジルコニウム
以下の実験はアルゴン雰囲気のグローブボックス中で行った。50mLのシュレンク管中、trans-1,2-ビス(2-ヒドロキシ-3,5-ジ-tert-ブチルベンジルスルファニル)シクロオクタン207mg(0.336mmol)をトルエン10mLに溶かし、この溶液に室温でテトラベンジルジルコニウム153mg(0.336mmol)のトルエン溶液10mLを滴下し、さらに1時間攪拌した。トルエンを減圧下留去し、残渣をヘキサン2mLで洗浄後乾燥し、無色結晶として表題化合物216mg(収率76%)を得た。
融点:181-183℃ 分解
1H-NMR (400 MHz,δ, ppm, C6D6)
1.16-1.80 (m, 48 H), 2.16 (d, J = 10Hz, 2 H), 2.42 (m, 2 H), 2.78 (d, J = 10Hz, 2 H), 3.16 (d, J = 14Hz, 2 H), 3.50 (d, J = 14Hz, 2 H), 6.61 (d, J = 2Hz, 2 H), 6.90 (t, J = 8Hz, 2 H), 7.09 (t, J = 8Hz, 4 H), 7.25 (t, J = 8Hz, 4 H), 7.52 (d, J = 2Hz, 2 H).
13C-NMR (100.4 MHz, δ, ppm, C6D6)
25.2, 26.1, 28.6, 30.6, 31.7, 34.2, 34.8, 35.7, 48.7, 64.0, 122.0, 123.1, 124.3, 126.2, 128.5, 128.7, 129.6, 140.9, 145.8, 158.0.
元素分析:計算値(C52H72O2S2Zr)C, 70.61%; H, 8.21%.
実測値:C, 70.54%; H, 8.31%.
[シクロヘキサンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム
以下の実験はアルゴン雰囲気のグローブボックス中で行った。100mLのシュレンク管中、trans-1,2-ビス(2-ヒドロキシ-3,5-ジ-tert-ブチルベンジルスルファニル)シクロヘキサン 200.0mg(0.342mmol)をトルエン10mLに溶かし、この溶液に室温でテトラベンジルハフニウム185.7mg(0.342mmol)のトルエン溶液10mLを滴下し、さらに1時間攪拌した。トルエンを減圧下留去し、残渣をヘキサン2mLで3回洗浄後乾燥し、無色結晶として表題化合物のジアステレオマー混合物として201.3mg(収率62%)を得た。ジアステレオマー比は、64/36であった。
Major:1H-NMR (400 MHz,δ, ppm, CD3C6D5)
1.06-1.92 (m, 44H), 2.55(d, J = 12.0Hz, 2H), 2.84(d, J = 12.0Hz, 2H), 3.21(d, J = 14.0Hz, 2H), 3.37(d, J = 14.0Hz, 2H), 6.62 (d, J = 2.4Hz, 2H), 6.74-6.81(m, 2H), 7.04-7.12(m, 6H), 7.25(d, J = 7.6Hz, 4H), 7.54 (d, J = 2.4Hz, 2H).
Minor:1H-NMR (400 MHz,δ, ppm, CD3C6D5)
1.06-1.92 (m, 44H), 2.38(d, J = 11.6Hz, 2H), 2.85(d, J = 14.0Hz, 2H), 2.94(d, J = 11.6Hz, 2H), 3.18(d, J = 14.0Hz, 2H), 6.59 (d, J = 2.4Hz, 2H), 6.74-6.81(m, 2H), 7.04-7.12(m, 6H), 7.31(d, J = 7.6Hz, 4H), 7.47 (d, J = 2.4Hz, 2H).
以下の実験はアルゴン雰囲気のグローブボックス中で行った。50mLのシュレンク管中、trans-1,2-ビス(2-ヒドロキシ-3,5-ジ-tert-ブチルベンジルスルファニル)シクロオクタン192mg(0.313mmol)をトルエン10mLに溶かし、この溶液に室温でテトラベンジルジルコニウム170mg(0.313mmol)のトルエン溶液10mLを滴下し、さらに1時間攪拌した。トルエンを減圧下留去し、残渣をヘキサン2mLで洗浄後乾燥し、無色結晶として表題化合物209mg(収率69%)を得た。
融点:203℃ 分解
1H-NMR (400 MHz,δ, ppm, C6D6)
1.18-1.94 (m, 48H), 2.35 (m, 2H), 2.61 (d, J = 12Hz, 2H), 2.88 (d, J = 12Hz, 2H), 3.13 (d, J = 14Hz, 2 H), 3.41 (d, J = 14Hz, 2 H), 6.62 (d, J = 2Hz, 2H), 6.78 (t, J = 8Hz, 2H), 7.10 (t, J = 8Hz, 4H), 7.29 (t, J = 8Hz, 4H), 7.57 (d, J = 2Hz, 2H)
13C-NMR (100.4 MHz, δ, ppm, C6D6)
25.1, 26.2, 28.8, 30.5, 31.8, 32.1, 34.2, 35.6, 49.1, 77.2, 121.4, 121.8, 124.6, 125.6, 126.0, 129.3, 138.5, 141.1, 148.4, 157.9.
元素分析:計算値(C52H72O2S2Hf)C, 64.27%; H, 7.47%.
実測値:C, 63.87%; H, 7.59%.
[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジクロロハフニウム
以下の実験はアルゴン雰囲気下で行った。100mLのシュレンク管中、trans-1,2-ビス(2-ヒドロキシ-3,5-ジ-tert-ブチルベンジルスルファニル)シクロオクタン1.00g(1.63mmol)をジエチルエーテル20mLに溶かし、この溶液にn-ブチルリチウム 2mL(1.65mol/l, 3.30mmol)を0℃で30分間攪拌した。この溶液を室温でテトラクロロハフニウム530mg(1.65mmol)のジエチルエーテル溶液50mLへと滴下し、さらに終夜攪拌した。生成した沈殿物を濾過して除き、濾液を減圧下濃縮した。残渣をペンタン5mLで洗浄後乾燥し、無色結晶として表題化合物558mg(収率40%)を得た。
1H-NMR (400 MHz,δ, ppm, C6D6)
0.54-1.86 (m, 48 H), 2.56 (br s, 2 H), 3.20 (d, J = 14Hz, 2 H), 4.35 (d, J = 14Hz, 2 H), 6.56 (br s, 2 H), 7.56 (br s, 2 H).
13C-NMR (100.4 MHz, δ, ppm, C6D6)
24.9, 26.1, 28.8, 30.4, 31.8, 34.3, 35.5, 36.0, 49.3, 120.3, 125.1, 125.7, 139.4, 142.1, 157.3.
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をベンゼン1mLとヘキサン5mLに溶かし、この溶液に25℃でトリス(ペンタフルオロフェニル)ボラン [B(C6F5)3] 10.2mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに10分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 0.62g(収率21%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)99.3%であり、Mw=120000、Mw/Mn=1.3であった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をベンゼン1mLとヘキサン5mLに溶かし、この溶液に25℃でトリス(ペンタフルオロフェニル)ボラン [B(C6F5)3] 10.2mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに20分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 1.20g(収率40%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)98.9%であり、Mw=185000、Mw/Mn=1.5であった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をベンゼン1mLとヘキサン5mLに溶かし、この溶液に25℃でトリス(ペンタフルオロフェニル)ボラン [B(C6F5)3] 10.2mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに30分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 2.16g(収率72%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)97.0%であり、Mw=227000、Mw/Mn=1.7であった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をベンゼン1mLに溶かし、この溶液に25℃でトリス(ペンタフルオロフェニル)ボラン [B(C6F5)3] 10.2mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに4分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 0.29g(収率10%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)99.2%であり、Mw=100000、Mw/Mn=1.3であった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をベンゼン1mLに溶かし、この溶液に25℃でトリス(ペンタフルオロフェニル)ボラン [B(C6F5)3] 10.2mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに7分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 0.95g(収率32%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)99.3%であり、Mw=170000、Mw/Mn=1.5であった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をベンゼン1mLに溶かし、この溶液に25℃でトリス(ペンタフルオロフェニル)ボラン [B(C6F5)3] 10.2mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに10分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 2.02g(収率67%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)98.9%であり、Mw=191000、Mw/Mn=1.8であった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をトルエン5mLに溶かし、この溶液に0℃でトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート[Ph3CB(C6F5)4] 18.4mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに15分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 0.76g(収率25%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)98.2%であり、Mw=256000、Mw/Mn=1.5であった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をトルエン5mLに溶かし、この溶液に0℃でトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート[Ph3CB(C6F5)4] 18.4mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに30分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 2.20g(収率73%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)99.7%であり、Mw=421000、Mw/Mn=1.6であった。
50mLのシュレンク管中、25℃で[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルジルコニウム17.7mg(0.020mmol)とトリス(ペンタフルオロフェニル)ボラン[B(C6F5)3] 10.2mg(0.020mmol)に無溶媒で1-ヘキセン3g(35.6mmol)を加え、さらに5分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 2.68g(収率89%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)95.3%であり、Mw=43000、Mw/Mn=1.9であった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルジルコニウム17.7mg(0.020mmol)をベンゼン1mLとヘキサン5mLに溶かし、この溶液に25℃でトリス(ペンタフルオロフェニル)ボラン [B(C6F5)3] 10.2mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに10分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 2.86g(収率95%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)97.6%であり、Mw=43000、Mw/Mn=1.9であった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルジルコニウム17.7mg(0.020mmol)をベンゼン1mLとヘキサン5mLに溶かし、この溶液に25℃でトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート[Ph3CB(C6F5)4] 18.4mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに10分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 2.90g(収率97%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)97.4%であり、Mw=41000、Mw/Mn=2.1であった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルジルコニウム17.7mg(0.020mmol)をベンゼン2mLとヘキサン10mLに溶かし、この溶液に25℃でトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート[Ph3CB(C6F5)4] 18.4mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に0℃で1-ヘキセン3g(35.6mmol)を加え、さらに10分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 2.76g(収率92%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)98.7%であり、Mw=120000、Mw/Mn=1.6であった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルジルコニウム1.8mg(0.0020mmol)をベンゼン1mLに溶かし、この溶液に25℃でトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート[Ph3CB(C6F5)4] 1.8mg(0.0020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに10分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 0.83g(収率28%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)97.9%であり、Mw=59000、Mw/Mn=1.7であった。
50mLのシュレンク管中、[シクロヘキサンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム18.9mg(0.020mmol)をベンゼン1mLとヘキサン5mLに溶かし、この溶液に25℃でトリス(ペンタフルオロフェニル)ボラン [B(C6F5)3] 10.2mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で1-ヘキセン3g(35.6mmol)を加え、さらに10分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 0.03g(収率1%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)86.2%であり、Mw=28400、Mw/Mn=1.9であった。
50mLのシュレンク管中、[シクロヘキサンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム18.9mg(0.020mmol)をトルエン5mLに溶かし、この溶液に25℃でトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート[Ph3CB(C6F5)4] 18.4mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に0℃で1-ヘキセン3g(35.6mmol)を加え、さらに15分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、70℃で揮発成分を真空ポンプを用いて留去し、ポリ(1-ヘキセン) 0.03g(収率1%)を得た。得られたポリ(1-ヘキセン)の立体選択性は13C-NMRよりアイソ選択性(mmmm)88.6%であり、Mw=56000、Mw/Mn=1.9であった。
以下の実験はアルゴン雰囲気のグローブボックス中で行い、分子量は<分子量測定条件2>、規則性は<規則性測定条件2>と<算出方法2>により求めた。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をベンゼン1mLとヘキサン5mLに溶かし、この溶液に25℃でトリス(ペンタフルオロフェニル)ボラン [B(C6F5)3] 10.2mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で4-メチル-1-ペンテン3g(35.6mmol)を加え、さらに5分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、白色固体を濾別し、70℃で真空下乾燥し、ポリ(4-メチル-1-ペンテン) 0.09g(3%)を得た。得られたポリ(4-メチル-1-ペンテン)の13C-NMRを測定したが、アイソ選択性(mmmm)以外のスペクトルは確認できなかった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をベンゼン1mLとヘキサン5mLに溶かし、この溶液に25℃でトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート[Ph3CB(C6F5)4] 18.4mg(0.020mmol)を加え、さらに5分間攪拌した。この溶液に25℃で4-メチル-1-ペンテン3g(35.6mmol)を加え、さらに5分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、白色固体を濾別し、70℃で真空下乾燥し、ポリ(4-メチル-1-ペンテン) 0.21g(7%)を得た。得られたポリ(4-メチル-1-ペンテン)の13C-NMRを測定したが、アイソ選択性(mmmm)以外のスペクトルは確認できなかった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をトルエン5mLに溶かし、この溶液に25℃でトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート[Ph3CB(C6F5)4]を加え、さらに5分間攪拌した。この溶液に25℃で4-メチル-1-ペンテン1g(11.9mmol)を加え、さらに10分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、白色固体を濾別し、70℃で真空下乾燥し、ポリ(4-メチル-1-ペンテン) 0.10g(10%)を得た。得られたポリ(4-メチル-1-ペンテン)の13C-NMRを測定したが、アイソ選択性(mmmm)以外のスペクトルは確認できなかった。
50mLのシュレンク管中、[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム19.4mg(0.020mmol)をジクロロメタン5mLに溶かし、この溶液に25℃でトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート[Ph3CB(C6F5)4]を加え、さらに10分間攪拌した。この溶液に25℃で4-メチル-1-ペンテン1.0g(11.9mmol)を加え、さらに5分間攪拌した。この反応溶液にメタノールを加えて反応を停止し、白色固体を濾別し、70℃で真空下乾燥し、ポリ(4-メチル-1-ペンテン) 0.34g(34%)を得た。得られたポリ(4-メチル-1-ペンテン)の13C-NMRを測定したが、アイソ選択性(mmmm)以外のスペクトルは確認できなかった。
熱分析装置 示差走査熱量計(Diamond DSC Perkin Elmer社製)を用いて下記の方法で測定した。
1)サンプル約10mgを窒素雰囲気下、220℃ 5分間保持
2)冷却 150℃~50℃(5℃/分)1分間保持
3)測定 50℃~180℃(5℃/分)
ゲルパーミエーションクロマトグラフィー(GPC)により、下記の条件で測定した。検量線は標準ポリスチレンを用いて作成した。分子量分布は重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)で評価した。
機種: ミリポアウオーターズ社製 150C型
カラム: TSK-GEL GMH-HT 7.5×600×2本
測定温度:152℃
溶媒: オルトジクロロベンゼン、
測定濃度:5mg/5mL
アイソタクチック・ペンタッド分率とは、A.Zambelliらによって「Macromolecules」、Vol.6、925(1973)に発表されている方法、すなわち13C-NMRを使用して測定される結晶性ポリプロピレン分子鎖中のペンタッド単位でのアイソタクチック連鎖、換言すればプロピレンモノマー単位が5個連続してメソ結合した連鎖の中心にあるプロピレンモノマー単位の分率である。10mmΦの試験管中で約200mgの重合体を3mLのオルトジクロロベンゼンに均一に溶解させて試料を調製し、その試料を13C-NMRスペクトルで測定した。核磁気共鳴装置(ブルカー社製AVANCE600)を使用し、以下の条件で測定された値である。NMR吸収ピークの帰属に関しては、F.A.Boveyらの「Macromolecules」、Vol.8、687(1975)に従った。
測定温度:135℃;
パルス繰り返し時間:10秒;
パルス幅:45°;
積算回数:2500回;
(4)固有粘度([η])(単位:dl/g)
ウベローデ型粘度計を用い、測定温度135℃にて溶媒にテトラリンを用いて測定した。
(d-MAOの調製方法)
3方コックを取り付けた攪拌子入りの200mL2口フラスコを窒素置換し、東ソー・ファインケム社製PMAO-Sトルエン溶液(アルミニウム含量6.1wt%)を100mLシリンジで測り取り、フラスコに投入した。この溶液を減圧し揮発成分を除去した。得られた白色固体を脱水トルエン100mLに再溶解した後、揮発成分を減圧除去した。この操作を更に2回繰り返し、白色粉末14.1gを得た。
(d-MMAO-3Aの調製方法)
東ソー・ファインケム社製PMAO-Sトルエン溶液(アルミニウム含量6.1wt%)を東ソー・ファインケム社製MMAO-3Aトルエン溶液(アルミニウム含量7.0wt%)にしたこと以外は参考例7と同様に実施した。
(d-MMAO-4の調製方法)
東ソー・ファインケム社製PMAO-Sトルエン溶液(アルミニウム含量6.1wt%)を東ソー・ファインケム社製MMAO-4トルエン溶液(アルミニウム含量7.4wt%)にしたこと以外は参考例7と同様に実施した。
内容積400mLの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、溶媒としてトルエン40mL、モノマーとしてプロピレン80gを仕込み、反応器を0℃まで降温した。降温後、d-MAO 118mgを投入し、続いて[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム(1μmol/mL、トルエン溶液)1mL(1.0μmol)を投入して重合を開始した。温度を0℃に保ちながら、60分間重合を行った。
重合の結果0.5gのポリプロピレンが得られた。重合活性5.0×105 g/mol、融点=156.2℃、Mw=50400、Mw/Mn=2.1、[mmmm]=93.7%であった。
重合温度を14℃にしたこと以外は実施例13と同様に実施した。
重合温度を40℃にしたこと以外は実施例13と同様に実施した。
重合温度を70℃にしたこと以外は実施例13と同様に実施した。
d-MAOをd-MMAO-3Aに重合温度を40℃にしたこと以外は実施例13と同様に実施した。
d-MAOをd-MMAO-4に重合温度を40℃にしたこと以外は実施例13と同様に実施した。
(実施例19)
内容積400mLの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、溶媒としてトルエン40mL、モノマーとしてプロピレン80gを仕込み、反応器を0℃まで降温した。降温後、d-MAO 118mgを投入し、続いて[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジクロロハフニウム(0.33μmol/mL、トルエン溶液)1.5mL(0.5μmol)を投入して重合を開始した。温度を70℃に保ちながら、60分間重合を行った。
重合の結果11.3gのポリプロピレンが得られた。重合活性2.3×107 g/mol、融点=139.7℃、Mw=16500、Mw/Mn=2.3、[mmmm]=85.4%、[η] = 0.22であった。
内容積400mLの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、溶媒としてトルエン40mL、モノマーとしてプロピレン80gを仕込み、反応器を40℃まで昇温した。昇温後、d-MAO 118mgを投入し、続いて[シクロヘキサンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム(0.456μmol/mL、トルエン溶液)1.1mL(0.50μmol)を投入して重合を開始した。温度を40℃に保ちながら、60分間重合を行った。
重合の結果1.5gのポリプロピレンが得られた。重合活性3.0×106 g/mol、融点=76.9℃、Mw= 6900 、Mw/Mn=1.7、[mmmm]=40.5%、[η] = 0.12、であった。
内容積400mLの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、溶媒としてトルエン40mL、モノマーとしてプロピレン80gを仕込み、反応器を40℃まで昇温した。昇温後、トリイソブチルアルミニウム (1.0mol/L、トルエン溶液)0.5mL(0.5mmol)を投入し、続いて[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム(1.85μmol/mL、トルエン溶液)2.7mL(5.00μmol)、さらに続いてトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート(4.0μmol/mL、トルエン溶液)6.25mL(25.00μmol)を投入して重合を開始した。温度を40℃に保ちながら、60分間重合を行った。
重合の結果17.1gのポリプロピレンが得られた。重合活性3.4×106 g/mol、融点=148.5℃、Mw= 31900 、Mw/Mn=2.4、[mmmm]=90.9%、[η] = 0.36であった。
内容積400mLの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、溶媒としてトルエン40mL、モノマーとしてプロピレン80gを仕込み、反応器を40℃まで昇温した。昇温後、トリイソブチルアルミニウム (1.0mol/L、トルエン溶液)0.5mL(0.5mmol)を投入し、続いて[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジクロロハフニウム(0.33μmol/mL、トルエン溶液)3.0mL(1.00μmol)、さらに続いてトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート(4.0μmol/mL、トルエン溶液)1.25mL(5.00μmol)を投入して重合を開始した。温度を40℃に保ちながら、60分間重合を行った。
重合の結果2.6gのポリプロピレンが得られた。重合活性2.6×106 g/mol、融点=140.0℃、Mw= 11800 、Mw/Mn=2.2、[mmmm]=86.4%、[η] = 0.18であった。
ハフニウム錯体量を5.0μmolに重合温度を40℃にモノマーを1-ブテンにしたこと以外は実施例13と同様に実施した。
重合の結果20.0gのポリブテンが得られた。重合活性4.0×106 g/mol、融点=107.0℃、Aw= 4190 、Mw/Mn=2.2、[mmmm]=96.0%であった。
内容積400mLの撹拌機付きオートクレーブを真空乾燥してアルゴンで置換後、溶媒としてトルエン40mL、モノマーとして1-ブテン80gを仕込み、反応器を40℃まで昇温した。昇温後、トリイソブチルアルミニウム (1.0mol/L、トルエン溶液)0.5mL(0.5mmol)を投入し、続いて[シクロオクタンジイル-trans-1,2-ビス(2-オキソイル-3,5-ジ-tert-ブチルベンジルスルファニル)]ジベンジルハフニウム(1.85μmol/mL、トルエン溶液)2.7mL(5.00μmol)、さらに続いてトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート(4.0μmol/mL、トルエン溶液)6.25mL(25.00μmol)を投入して重合を開始した。温度を40℃に保ちながら、60分間重合を行った。
重合の結果7.7gのポリブテンが得られた。重合活性1.5×106 g/mol、融点=107.7℃、Aw=1900、Mw/Mn=2.0、[η] = 0.45、[mmmm]=96.1%であった。
Claims (10)
- nが3である請求項1に記載の触媒。
- R1及びR2が、独立に、置換基を有してもよい炭素数1~30のアルキル基である、請求項1または2に記載の触媒。
- 助触媒としてホウ素化合物または有機アルミニウム化合物をさらに含有する請求項1~3のいずれか1項に記載の触媒。
- ホウ素化合物が、BR11R12 R13、W+ (BR11 R12 R13R14 )-または(V-H)+ (BR11 R12 R13R14 )-である、請求項4に記載の触媒。
(式中、R11~R14 はハロゲン原子、1~20個の炭素原子を含むハイドロカルビル基、
1~20個の 炭素原子を含むハロゲン化ハイドロカルビル基、
1~20個の炭素原子を含む置換シリル基、
1~20個の炭素原子を含むアルコキシ基または2~20個の炭素原子を含む2置換アミノ基であり、
それらは同じであっても異なっていても良く、
W+ は無機または有機のカチオンであり、
Vは中性ルイス塩基であり、(V-H)+ はブレンステッド酸である。) - 有機アルミニウム化合物が、環状のアルミノキサンおよび/または線状のアルミノキサンである、請求項4に記載の触媒。
- 請求項1~6のいずれかに記載の触媒の存在下にオレフィンを重合させることを含む、立体選択的ポリオレフィンの製造方法。
- オレフィンがモノオレフィンまたはジオレフィンである請求項7に記載の製造方法。
- モノオレフィンが、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、および4-メチル-1-ペンテンから成る群から選ばれる少なくとも1種のオレフィンである請求項8に記載の製造方法。
- ジオレフィンが、ブタジエン、1,5-ヘキサジエンおよび1,6-ヘプタジエンから成る群から選ばれる少なくとも1種のオレフィンである請求項8に記載の製造方法。
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CN2011800090835A CN102844337A (zh) | 2010-02-12 | 2011-02-10 | 立体选择烯烃聚合用催化剂和立体选择聚烯烃的制造方法 |
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PCT/JP2011/052938 WO2011099584A1 (ja) | 2010-02-12 | 2011-02-10 | エチレン系重合用触媒及びエチレン系重合体の製造方法 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2012111780A1 (ja) * | 2011-02-18 | 2012-08-23 | 住友化学株式会社 | オレフィン重合用触媒及びオレフィン重合体の製造方法 |
WO2013022102A1 (ja) * | 2011-08-11 | 2013-02-14 | 住友化学株式会社 | エチレン系重合用触媒およびエチレン系重合体の製造方法 |
WO2013022108A1 (ja) * | 2011-08-11 | 2013-02-14 | 住友化学株式会社 | オレフィン重合用触媒及びオレフィン重合体の製造方法 |
WO2013022103A1 (ja) * | 2011-08-11 | 2013-02-14 | 住友化学株式会社 | 4族遷移金属錯体を用いるオレフィンブロックポリマーの製造方法 |
CN110612313A (zh) * | 2017-03-23 | 2019-12-24 | 埃克森美孚化学专利公司 | 催化剂体系及其制备和使用方法 |
Families Citing this family (6)
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WO2012111779A1 (ja) * | 2011-02-18 | 2012-08-23 | 住友化学株式会社 | エチレン系重合用触媒及びエチレン系重合体の製造方法 |
WO2012111778A1 (ja) * | 2011-02-18 | 2012-08-23 | 住友化学株式会社 | オレフィン重合用触媒及びオレフィン重合体の製造方法 |
CN103958548B (zh) * | 2011-12-02 | 2016-05-18 | 住友化学株式会社 | 使用多种过渡金属催化剂的烯烃嵌段聚合物的制造方法 |
CA3041067A1 (en) * | 2016-10-27 | 2018-05-03 | Univation Technologies, Llc | Method of preparing a molecular catalyst |
BR112023000804A2 (pt) * | 2020-07-17 | 2023-02-07 | Dow Global Technologies Llc | Processos para polimerizar monômeros de olefina e de polimerização |
CN116234834A (zh) * | 2020-07-17 | 2023-06-06 | 陶氏环球技术有限责任公司 | 双苯基苯氧基金属-配体络合物的烃基改性甲基铝氧烷助催化剂 |
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AU2003247806B2 (en) | 2002-07-08 | 2009-11-12 | Genentech, Inc. | Compositions and methods for the treatment of immune related diseases |
WO2007075299A2 (en) | 2005-12-16 | 2007-07-05 | Dow Global Technologies Inc. | Polydentate heteroatom ligand containing metal complexes, catalysts and methods of making and using the same |
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- 2011-02-10 CN CN2011800090303A patent/CN102791745A/zh active Pending
- 2011-02-10 JP JP2011553902A patent/JPWO2011099584A1/ja active Pending
- 2011-02-10 WO PCT/JP2011/052937 patent/WO2011099583A1/ja active Application Filing
- 2011-02-10 WO PCT/JP2011/052938 patent/WO2011099584A1/ja active Application Filing
- 2011-02-10 US US13/577,933 patent/US20130059991A1/en not_active Abandoned
- 2011-02-10 US US13/577,952 patent/US20130035462A1/en not_active Abandoned
- 2011-02-10 CN CN2011800090835A patent/CN102844337A/zh active Pending
- 2011-02-10 DE DE112011100521T patent/DE112011100521T5/de not_active Withdrawn
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JP2005523952A (ja) * | 2002-04-24 | 2005-08-11 | ビーピー ケミカルズ リミテッド | 重合触媒 |
JP2003327612A (ja) * | 2002-05-09 | 2003-11-19 | Sumitomo Chem Co Ltd | 重合用触媒およびオレフィン系重合体の製造方法 |
JP2006516668A (ja) * | 2003-02-07 | 2006-07-06 | バーゼル、ポリオレフィン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング | 重合触媒、有機遷移金属化合物、ポリオレフィンの製造方法及びポリオレフィン |
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WO2012111780A1 (ja) * | 2011-02-18 | 2012-08-23 | 住友化学株式会社 | オレフィン重合用触媒及びオレフィン重合体の製造方法 |
WO2013022102A1 (ja) * | 2011-08-11 | 2013-02-14 | 住友化学株式会社 | エチレン系重合用触媒およびエチレン系重合体の製造方法 |
WO2013022108A1 (ja) * | 2011-08-11 | 2013-02-14 | 住友化学株式会社 | オレフィン重合用触媒及びオレフィン重合体の製造方法 |
WO2013022103A1 (ja) * | 2011-08-11 | 2013-02-14 | 住友化学株式会社 | 4族遷移金属錯体を用いるオレフィンブロックポリマーの製造方法 |
US9593194B2 (en) | 2011-08-11 | 2017-03-14 | Sumitomo Chemical Company, Limited | Method for producing olefin block polymer using group 4 transition metal complex |
CN110612313A (zh) * | 2017-03-23 | 2019-12-24 | 埃克森美孚化学专利公司 | 催化剂体系及其制备和使用方法 |
Also Published As
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US20130059991A1 (en) | 2013-03-07 |
DE112011100521T5 (de) | 2012-11-29 |
CN102844337A (zh) | 2012-12-26 |
US20130035462A1 (en) | 2013-02-07 |
DE112011100520T5 (de) | 2012-11-29 |
WO2011099584A1 (ja) | 2011-08-18 |
CN102791745A (zh) | 2012-11-21 |
JPWO2011099584A1 (ja) | 2013-06-17 |
JPWO2011099583A1 (ja) | 2013-06-17 |
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